Hydrocarbyl sulfenylmercapto pyrimidines used as pesticides

ABSTRACT

Compounds of the formula   D R A W I N G wherein R, R1 and R2 are hydrogen, halogen, hydroxyl, alkyl or alkenyl optionally substituted with halogen atoms and R3 is an aliphatic hydrocarbyl group or an aryl group or   wherein R4 is hydrogen or alkyl and R5 is hydrogen, alkyl, alkenyl or phenyl optionally substituted with halogen atoms, and n is 0 or 1, possess fungicidal and insecticidal activity.

United States Patent [191 Moore HYDROCARBYL SULFENYLMERCAPTO PYRIMIDINES USED AS PESTICIDES Related US. Application Data [62] Division of Ser. No 20l,l85, Nov. 22, i971, Pat. No,

[52] U.S. Cl. 424/251 [51] Int. Cl. ..AO1N 9/00; AOln 9/22 [58] Field of Search 424/25 l; 260/2565 R [56] References Cited UNITED STATES PATENTS 2,839,446 6/l958 Margot et al. 260/251 R Primary Examiner-Stanley J. Friedman Assistant Examiner-Douglas W. Robinson Attorney, Agent, or Firm-J. A. Buchanan, Jr.; John Stoner, Jr.; Raymond Owyang [57] ABSTRACT Compounds of the formula July 22, 1975 wherein R, R and R are hydrogen halogen, h droxyl, alkyl or alkenyl optionally substituted with hal ogen atoms and R is an aliphatic hydrocarbyl group or an aryl group or wherein R is hydrogen or alkyl and R" is hydrogen, alkyl, alkenyl or phenyl optionally substituted with halogen atoms. and n is 0 or i. possess fungicidal and insecticidal activity.

[0 Claims, N0 Drawings This is a division of application Ser. No. 20l,l85, filed Nov. 22, l97l now U.S. Pat. No. 3,82l,222.

BACKGROUND OF THE INVENTION l. Field The present invention is directed to hydrocarbyl sulfenylmercapto pyrimidines and their use as fungicides and juvenile hormone mimetic insecticides.

2. Prior Art U.S. Pat. No. 2,839,446 discloses certain pyrimidine derivatives, particularly trichloromethyl sulfenylmercapto pyrimidines and their use in the control of fungi.

DESCRIPTION OF THE INVENTION The present invention is directed to certain novel pyrimidine compounds and the use of certain pyrimidine compounds for the control of fungi and insects. Certain of the pyrimidines mimic the activity of juvenile hormone.

The novel compounds of the present invention can be represented by the general formula wherein R, R and R are individually hydrogen, halogen of atomic number 9 to 35 (fluorine, chlorine or bromine), hydroxy, alkyl of l to 6 carbon atoms substituted with to 4 halogen atoms of atomic number 9 to 35 or alkenyl of 2 to 6 carbon atoms substituted with O to 4 halogen atoms of atomic number 9 to 35, R is an aliphatic hydrocarbyl group (i.e., alkyl or alkenyl) of 2 to l0 carbon atoms substituted with l to halogen atoms of atomic number 9 to 35, aryl of 6 to 12 carbon atoms substituted with 0 to 2 halogen atoms of atomic number 9 to 35 or alkyl groups of 1 to 4 carbon atoms,

wherein R is hydrogen or alkyl of 1 to 4 carbon atoms and R is hydrogen, alkyl of l to 4 carbon atoms, alke nyl of 2 to 4 carbon atoms or phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to 35, and n is O or 1.

Preferably R' is hydrogen, R and R are, individually, hydrogen, hydroxy or alkyl of l to 4 carbon atoms and R is alkyl of 2 to 4 carbon atoms substituted with l to 5 halogen atoms of atomic number 9 to 35, particularly chlorine, or phenyl substituted with O to 2 halogen atoms of atomic number 9 to 35, particularly chlorine, or

u N CR wherein R is alkyl of l to 4 carbon atoms and R is hydrogen. More preferably, R is hydrogen or methyl, R is hydrogen, R is hydrogen, hydroxy or alkyl of l to 3 carbon atoms and R is alkyl of 2 to 4 carbon atoms substituted with 2 to 5 chlorine atoms or phenyl substituted with l to 2 chlorine atoms. The most preferred R groups are the tetrachloroethyl. l,l-diemthyl-2,2- dichloroethyl, p-chlorophenyl or wherem R IS ethyl and R is hydrogen.

The above novel compounds are useful in the control of fungi. Also, the above novel compounds are useful insecticides. In fact, the compounds described above possess juvenile hormone mimetic activity. In particular the compounds wherein R is an aliphatic hydrocarbyl group of l to ID carbon atoms substituted with l to 5 halogen atoms of atomic number 9 to possess juvenile hormone mimetic activity. Thus compounds wherein R is methyl substituted with halogen atoms also have juvenile hormone mimetic activity.

Representative compounds which R, R. and R may represent are hydrogen, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, ally], crotyl, 2- propenyl, chloromethyl, trichloromethyl, bromomethyl, 2-fluoroethyl, etc.

Preferably the representative groups for R, R and R will be hydrogen, hydroxy, methyl, ethyl, propyl and butyl.

Representative groups which R may represent include l-chloroethyl, l, l -dichloroethyl, l ,l ,2- trichloroethyl, 2,2,2-trichloroethyl, l,l,2,2-tetrachloroethyl, l,2,2,2-tetrachloroethyl, pentachloroethyl, trichlorovinyl, l,l dimethyl-2,2,2-trichloroethyl, l, l -dimethyl-2,2-dichloroethyl, l,l ,2,2-tetrachloropropyl, l,2,3-trichloropropyl, l,l-difluoroethyl, l,l,2- tribromoethyl, l-bromo-2-chloroethyl, l, l dichlorohexyl, phenyl, naphthyl, 4-chlorophenyl, 2- chlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2-bromophenyl, 3-fluorophenyl, 2-methyl-4- chlorophenyl, 4-butylphenyl, etc.

Representative groups which R may represent include methyl, ethyl, n-propyl, isopropyl, n-butyl, tbutyl, etc.

Representative groups which R may represent include hydrogen, methyl, ethyl, propyl, butyl, allyl, vinyl, phenyl, o-chlorophenyl, o,p-difluorophenyl, etc.

When the compounds are used as insecticides, R may also represent chloromethyl, dichloromethyl, trichloromethyl, bromochloromethyl, trifluoromethyl, dibromomethyl, etc.

Typical compounds of the present invention include the following: 2-( l,l,2,2- tetrachloroethylsulfenylmercapto)-4-methyl pyrimidine, 2-( l,l ,2,Z-tetrachloroethylsulfenylmercapto )-4- chloromethyl-o-hydroxy pyrimidine, 2-( l l ,2,2- tetrachloroethylsulfenylmercapto)-4,6-dimethyl py- 3 rimidine. 2 l .l .2.2tetrachloroethylsulfenylmereap to)-4-chloro pyrimidine, 2 l.l.2.2-

tetrachloroethylsulfenylmercapto|-4.5.6-trimethyl pyrimidine. 2-( l l .2.Z-tetrachloroethylsulfenylmercapto)-4-hydroxy pyrimidine. 2( l.l 2.2- tetrachloroethylsulfenylmercaptol-4-hydroxy6-mcthyl pyrimidine. 2-( l.l .2.2- tetrachloroethylsulfenylmercapto)-4-ethyl-6-methyl pyrimidine. 2-( l .1 .2.2-tetrachloroethylsulfenylmercapto)-4-allyl pyrimidine, 2-( l.l .2.2 tetrachloroethylsulfenylmercapto)-4-hydroxy-fi-ethyl pyrimidine, 2-( 1.1.2.2- tetrachloroethylsulfenylmercapto )-4-hydroxy-6-nbutyl pyrimidine. 2-( [.1 .2.2

tetrachloroethylsulfenylmercapto)-4-methyl-6-crotyl pyrimidine, 2-( l l .2.2-tetrachloroethylsulfenylmercapto)4-propyl pyrimidine. 2-( 1.1.2 trichloroethylsulfenylmercapto)-4-methyl pyrimidine. 2 l .2.2.2-tetrachloroethylsulfenylmercapto)-4 methyl-6-hydroxy pyrimidine, 2- pentachloroethylsulfenylmercapto-4-methyl pyrimidine. 2( l l -dibromo-2.2- diehloroethylsulfenylmercapto)-4-hydroxy-6-methyl pyrimidine. Z-trichlorovinylsulfenylmercapto-4,6- dimethyl pyrimidine. 2-( 1.2- dichlorovinylsulfenylmercapto )-4.6-diethyl pyrimidine. 2-( 1.1 .2.2tetrachloropropylsulfenylmercapto)- 4-hydroxy pyrimidine. 2-(l.2.3-trichloropropylsulfenylmercapto) pyrimidine. 2-( 1.2.3- trichloropropylsulfenylmercapto)-o -ethyl pyrimidine. 2-pentachloroethylsulfenylmercapto-4-methyl-fiisopropyl pyrimidine. 2-( l .l-dimethyl-2.2- dichloroethylsulfenylmercapto)-4-propyl pyrimidine. 2-( I .l-dimethyl-2.2,-dichloroethylsulfenylmercapto 4-hydroxy-6-methyl pyrimidine. 2-(l.l-dimethyl-2.2- dibromoethylsulfenylmercapto)-4-butyl pyrimidine. 2-( l .l .2.2tetrachloroethylsulfenylmercapto) pyrimidine. 2 (phenylsulfenylmercapto)- 4.5-dimethyl pyrimidine. 2-(4 chlorophenylsulfenylmercapto)4-methyl- (i-hydroxy pyrimidine. 2-(4-chlorophenylsulfenylmercapto)-4-ethyl pyrimidine. 2-(4- chlorophenylsulfenylmercapto)-6-hydroxy pyrimidine. 2-(4-chlorophenylsulfenylmercapto)-4.5.6-trimethyl pyrimidine. 2-t4ehlorophenylsulfenylmercapto)-4- allyl pyrimidine. 2(3,4- dichlorophenylsulfenylmercapto)-4-methyl-6-hydroxy pyrimidine. 2-(3-methylphenylsulfenylmercapto)-4- hydroxy-6-methyl pyrimidine. 2-(2-fluoro-4- chlorophenylsulfenylmercapto)-4-methyl pyrimidine. 2-( 2 rnethyl-4-chlorophenylsulfenylmercapto) 4 hydroxy pyrimidine. 2- trichloromethylsulfenylmercapto l-4-hydroxy6-methyl pyrimidine. N-ethyl-N-(4.6-dimethylpyrimidoQ sulfenylmercapto) formamide, N-methylN-(4-hydroxy 6- methylpyrimidoJ-sulfenylmercapto) formamidc. N- propyl-N lJ-ethyl-o-vinylpyrimido-Z-sulfenylmer- 4 captoj formamide. N-cthylN-(4,6-dimethylpyrimido- Z-sulfenylmercapto) acct-amide. N-methyl'N-(4- hydroxy-o-chloropyrimido2sulfenylmcrcapto) benzamide. etc.

The hydrochlorides of the above-named compounds are also included.

The compounds of this invention are prepared by the reaction of a halogenated hydrocarbyl sulfenylchloride or an amido sulfenylchloride and an appropriate 2- mercapto pyrimidine or Z-mercapto pyrimidine hydrochloride. The reaction may be written as follows:

wherein R. R. R and R are as previously defined. When the 2-mercapto pyrimidine starting material is the hydrochloride salt two moles of hydrogen chloride are released during the reaction.

The reaction is usually carried out in a solvent. The reaction involving 2-mercapto pyrimidine may be carried out in dichloromethane. chloroform. benzene. xy lene. ethyl acetate or a liquid carboxylic acid. The reaction involving a Z-mercapto pyrimidine hydrochloride is preferably carried out in acetic acid as the solvent. The quantity of solvent is not critical and generally varies in weight from 5 to 50 times the weight of the pyrimidine compound. Usually the pyrimidine compound is dissolved or slurried in the solvent. and then unsolvated halogenated hydrocarbyl sulfenylchloride in an amount at least equal in moles to the pyrimidine is added rapidly. The reaction temperature may vary from 20 to 100C. In order to completely remove the byproduct hydrogen chloride. a temperature of to 100C. is preferred. When a hydrochloride product is desired. the reaction temperature is kept lower. e.g.. below C. The time of reaction is dependent upon the temperature and the nature of the reactants. however. reaction is continued until all of the insoluble starting material has disappeared. Usually the reaction is complete in from 0.1 to l0 hours. more often 0.5 to 1 hour.

The product is recovered from the reaction mixture by filtering hot and then evaporating off the solvent. The resulting crude product may be used as is. or it may be purified by crystallization or by chromatography. Crystallization is readily accomplished by cooling a solution of the crude product. Solvents for crystallization are preferably mixtures of aromatic hydrocarbons such as benzene. toluene. etc. with an aliphatic hydrocarbon such as pentane. hexane. etc. The ratio of the two may vary from [:2 to 2:l by volume.

The compounds of this invention may also be prepared by the process of U.S. Pat. No. 2.839.446. which is concerned with the Z-trichloromethyl sulfenylmercapto pyrimidines.

The subject invention can be more fully understood by reference to the following examples. Unless otherwise indicated percentages are by weight.

+ HCl EXAMPLE 1 Preparation of 2-( l ,l ,2.2-tetrachloroethylsulfenylmercapto)-4-methyl 5 pyrimidine A suspension was prepared by mixing 3.4 g. (0.02 mole) 2-mercapto-4-methyl pyrimidine hydrochloride in 100 ml. of acetic acid. Then 5.0 g. (0.02 mole) oftet- To a slurry of 5.0 g. (0.029 mole) of 2-mercapto-4- hydroxy-6-propyl pyrimidine in 50 ml. of 1.2- dimethoxyethane. was added 6.9 g. (0.029 mole) of l.- l.2,2-tetrachloroethylsulfenylchloride. The resulting mixture was heated at the reflux temperature for ten minutes, and then filtered while still hot. The solvent was removed by evaporation under reduced pressure to give 8.8 g. of 2-( 1.1.2.2- tetrachloroethylsulfenylmercapto)-4-hydroxy6-propyl rachloroethylsulfenylchloride was added to this suspen- K l igg ygfc g fi l g H llmelung of sion all at once. The resulting mixture was stirred at the 0 reflux temperature for 3 minutes. At the end of this time the reaction mixture was filtered while hot. The filtrate was evaporated to ml. by volume. This mate- H Calculated Found rial was then diluted with 100 ml. of benzene and 75 i a W M X M U ml. of hexane and cooled to 0C. The precipitate was 5 q 5: 5: removed by filtration and discarded. The filtrate was evaporated to give a liquid which crystallized upon standing. The crystals were separated by filtration and Infrared analysis showed strong adsorption bands at after drying weighed 3.3 g. The product. -(LL J- 6.15. 6.35. 6.75. 7.2, 7.65. 11.7, 12.4 and 13.3 mitetrachloroethylsulfenylmercapto)-4-methyl pyrimicrons, dine, had a melting point of 5456C. Analysis was as Other compounds of the present invention were follows: made by similar reactions. These are listed in Table 1.

TABLE l Elemental Analysis "/1 Melting Calculated Found Point Compound Cl N S Cl N S T.

2-(4-chlorophcnylsulfenylmcrcapto 13. 23.8 14.4 23.1 804(2 4-mcthyl pyrimidine 2-(1,2.2.24etrachlorocthylsuIfenyl- 45.7 20.] 45.4 30.5 -51 mercapto) pyrimidine 2-( l, l .2,2-telrachloroethylsulfcnyl- 45.7 20.1 46.3 20.5 89-90 mercapto) pyrimidine 2( 1.1.2,2-tetrachloroethylsulfenyl- 8.3 7.6 53-54 mercapto)-4,6-dimcthyl pyrimidine 2-( l.l-dimethyl2.2dichloroethyl- 33.1 20.0 29.6 19.4 200(dce) sulfenylmercapto)-6-hydroxy pyrimidine hydrochloride 2-( 1,1-dimethyl-2.Z-dichloroethyl- 23.9 21.6 24.4 21.6 82.5-8 3.5 sulfenylmercapto)-4,6-dimethyl pyrimidine 2-( l l -dimethyl-2,2-dichloroethyl- 17.6 29.6 17.5 29.3 [44-171 sulfenylmercapto)-4-propyl6hydroxy (dee) pyrimidine hydrochloride 2-( l,l,2.2-tetrachloroethylsulfenyl- 48.9 17.7 47.1 17.0 1 16-126 mercapto J-6-hydroxy pyrimidine hydrochloride 2-( 1,2,2.2-tetrachloroethylsulfenyl- 43.77 19.79 43.60 18.65 Oil mercapto )-4-methy1 pyrimidine 2-( l ,l-dimethyl-2,Z-dichlorosulfenyl- 25.04 22.64 26.75 21.48 Oil mercapto)-4-methyl pyrimidine N-ethyl-N-4,6-dimethylpyrimido-2- 1 7.3 26.4 Oil sulfenylmercapto) formamide UTlLlTY 55 Calculaed Found The novel compounds of the present invention ex- 0 4 43 8 hibit fungicidal activity against a variety of fungi. The

. 43. S N8 5 following examples indicate the fungicidal actwrty.

Example A The infrared spectra had strong adsorption bands at The Compounds were evaluated for fungi 6.35, 6.8, 7.5, 8.3, 12.0, 12.45, 13.2 d [405 p crdal effectiveness by means of the mycelial drop test. crons. This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhi- EXAMPLE 2 hition on mycelium growth. Each compound to be Preparation of 2-( l l .2.2-tetrachloroethylsulfenylmercapto)-4' hydroxy-6-propyl pyrimidine hydrochloride tested was dissolved in acetone to 250 ppm concentra tion. Paper discs previously inoculated with equal amounts of particular fungus mycelium were placed on 7 8 potato dextrose agar medium. The paper discs were TABLE III treated by applying a precise and equal volume of each of these fungicidal solutions to the center. Following 2 r}:

1'. C treatment with the fungitoxic chemical. the discs were Compound l'ruciisoliini incubated along with inoculated but untreated control 5 Q0111 discs a umbmnt temperatures until Such time that the 2-1l.l.1.Z-tetrachloroethylsulfenyl- Hi0 ltlll mycelial growth away from the edge of the untreated nierCapto)-4-methyl pyrimidine control discs reached a certain distance. From this I mercaptol-4-hydroxy-6-propyl pyrimidine comparison a percent inhibition oi growth area was dehydmchimidc termined. The results of these tests for various Coml0 4fi-qal p y l'lml Int? pounds of thls mvennon on parucular fungus myce' 8h l.2.1.3-tetrachlorocthylsuli'enylllIU ltll] lium are indicated in Table II nicrCzlptiil pyrimidine TABLE ll '71 Control P thium Helminthosporium Fusarium Rhizoctonia Compound u timum sativum oxysporum solani 14 l.l,2.2-tclrachlorocthylsulfenyl- 9h 98 78 I00 mercaptoJ-d-mcthyl pyrimidine 2-( l.l 2,2-tetrachloroethylsulfenyllot) mereapto i-d-hydroxy h-propyl pyrimidine hydrochloride 2-( l.2v2.2tctrachloroethylsulfcnyl- 78 mcrcapto) pyrimidine 2-( l.l.22Jetrachloroethylsull'cnyl- IUU '99 99 I00 mercapto) pyrimidine 2-( Ll .2.Z-tetrachloroethylsulfcnylllll) 99 i ll)() mcrcapto )Ab-dimcthyl pyrimidine 2-( lel-dimethyl-ZZ-dichloroethylor sulfenylmercapio l-4 hdimethyl pyrimidine -l l.l-dimethyl-2.2-dichloroethyl 85 suli'enylniercapto)4-propyl-6'h droxy pyrimidine hydrochloride 2-( l2.2.Z-ietrachloroethylsulfcnyl- 78 mercaptoi-4-methyl pyrimidine N-methyl-N-t4.6-dimethylpyrimido-2- 78 70 sull'enylmercaptol formamide Z-( l.l.2.Z-tetrachloroethylsulfenyl- [U0 )(1 70 mercapto)-6-hydroxy pyrimidine hydrochloride Example B 2-( l.l.ll tetraehloroethylsulfenyl- 100 I00 mercaptol pyrimidine A number of the compounds were also treated for ef- 24 Ll .3.Idetraghlorzc i j y IOU I00 mercapto)-4.oimct ylpyriirii ine fectiveness against spores by means of a variation of M1 1240mmlcromhylsumnyb M "The Standard Spore Slide-Germinatton Method for mercapio)6-hydroxy pyrimidine hydrochloride Determining Fungicidal Activity. described in the H l 2224mmhmmcmylsulfcFL Hm American Phyropailiulogit-al Society Journal. Volume 0 mcfgup9] 4.n1c1hyl pyrimidine 33, pages 627632 (I943). The method is designed to i'1 siillenylmcrcaptol-4-niethyl pyrimidine measure the fungitoxic activity of fungicidal chemicals. 4 m lp i mu mu their activity being expressed in terms of percent inhiy i l formiimldv bition of germination of fungus spores. Each compound toxicant to be tested was dissolved in acetone to a con- 55 w uscd as fungicides the compounds f his @emwhpn st 100 Pp These g q were p l/ention will be formulated and applied in fungicidal P the wells of depressloh Shdes and allowed {amounts by conventional art methods to fungi or hosts to y" h wells were filled Whh 3 Spore Suspension of which are subject to fungus attack. especially vegetalhe spficlfi'ed lest Organism A 10-fold greater vohhhe iive hosts such as plants. plant seeds, etc. The amount of Suspehsmh was used than that used to pp y the M) used will, of course. depend upon several factors such cant so that the slide concentration of toxicant was 10 ppm. The spores were then incubated in a moist chamber overnight. A group of I00 spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percent germination inhibition. Table lll reports the results of this testing.

as the host. the type of fungus. the particular compound. ctc. The amount generally will range from 2 to 90%. The compounds may be combined with inert liquids or solid carriers as powders. solutions, dispersions,

i; etc. for such use.

The compounds of this invention will generally be admixed with biologically inert liquids or solids in an amount of from about 0.005 to 95 weight percent. Higher or lower amounts can be used to advantage. Preferably from i to 50 weight percent of the composition will be the compound. Typical of the liquid carrier which may be admixed with the compounds of this in vention include, in addition to acetone, such liquids as water, kerosene, xylene. alcohols, alkylated naphthylene and glycols. Typical solids which may be incorpo rated with the compounds include the natural clays. such as kaolin clays, diatomaceous earth, synthetic fine silica, talc, pyrophyllite, etc.

Fungicidal formulations may also contain stabilizers, spreading agents, sticking agents, fillers, other compatible pesticides and the like.

The compounds of the present invention also exhibit insecticidal activity, particularly juvenile hormone mimetic activity. The following tests were conducted to show the juvenile hormone activity.

Example C To show the insecticidal activity of the subject compounds, particularly the juvenile hormone mimetic activity, several different pests in a preadult stage of development were contacted with a solution of the test compound. The treated insects were then observed as to the compounds effect upon the development of the succeeding stages (juvenilization), including egg laying and egg hatching to give a new generation. Mortality readings were taken.

Tests were carried out on the following pests: Dock Beetle (Gastmplzysa cyanes), Cabbage Looper (Trichvplusia ni) and Yellow Fever Mosquito (Aedes aegypn').

For the Dock Beetle test, an acetone solution containing 20 micrograms in l microliter of solution was topically applied to the abdomen of a late fifth stage (last stage) larva. Usually to 20, preferably 20, larvae were treated. Following treatment the larvae were kept in an incubator until the adult emerged (or at tempted to emerge). At this time a count was made of the dead pupae. The live specimens were examined under a microscope for juvenilization. The number of juvenile adults per total number tested was recorded, and is given in Table IV as percent juvenilization. Also the degree ofjuvenilization was measured based on the Percent control, defined as the percentage of treated insects which failed to perpetuate themselves. was also measured. In determining percent control, account was made of treated insects that failed to reach adulthood for one reason or another, plus those that failed to lay eggs, or that layed sterile eggs.

For the Cabbage Looper, an acetone solution containing 100 micrograms of the test compound in 5 microliters of solution was applied topically to the entire length of the body of a late fifth stage larva. Normally l0 larvae were treated per test. The treated larvae were then fed until they pupated. The pupae were examined under a microscope, checking for any larvae characteristics in the pupae (juvenilization). Percent juvenilization as well as mortality readings were made. The pupae were incubated until the adult (if any) emerged. These adults were then checked as to egg laying and percent laying fertile eggs. Mortality of the adults was determined. .luvenilization, degree of juvenilization and percent control were determined. The degree of juvenilization was measured based on the following:

0 normal appearing pupa l 1/2 larva l/2 pupa; no prolegs; pupoid thorax 2 1/2 larva l/Z pupa: prolegs; pupoid thorax 3 supernumery larva For the Yellow Fever Mosquito. late fourth stage lar- 5 vae of the mosquitos were placed in a cup containing 30 ml. of deionized water having 6 ppm of the test material dissolved therein. About 20 larvae were used per test. The larvae were fed and allowed to pupate. The pupae were examined under a microscope for retention of larvae characteristics (juvenilization). The live pupae were kept until the adult mosquito emerged. mated and layed eggs. The percent fertile eggs was determined. A count was made at each stage for mortality, i.e. larvae, pupae and adult.

chloroethylsulfenylmercapto)-4,6-dimethyl pyrimidine following. The results of the tests are tabulated in Table IV.

TABLE IV Dock Beetle Cabbage Looper Yellow Fever Mosquito .luve- Juve- Juvenili niliniliit Cone. zation Con- Conc. zation Conzation Conug/ trol p.31 trol Co nc. trol Compound insect) (Degree) (l) insect) (Degree) l) (ppm) (Degree) l 2-( l.l,2,2-tetrachloro- (4) i0 30 (L6) 6.6 0 (0) I00 ethylsulfenylmercapto 4-methyl pyrimidine 2-( l,l.2,2-tetrachloro- I00 0 70 ethylsulfenylmerc apto )-4- hydrox -6-propyl pyrimidine hydroc loride 2-( l,2,2.2-tetrachloro 100 20 (l) 100 ethyls ulfe nylmercapto pyrimidine 2-( l ,l,2,2-tetrachlorolOU 80 l 80 ethylsulfenylmercapto) pyrimidine 2-( 1,1 ,2,2-tctrachloro- 2O 60 3(1 100 1.5) I00 15 0 9U ethylsulfenylmercapto)- 4,6-dimethyl pyrimidine 2-( l ,l-dimethyl-2,2-di- 20 50 250 30 TABLE lV (onlinued Dock Beetle Cabbage Looper Ycllou Fever Mosquito Juve- .Imc- Jumnili "i nili 9i nili- 9i (onev zation Con Cone. zation (onlation Con- (ugf 7r trol (#gf 1/ trol Cone. A trol Compound insect) (Degree) l insect! (Degree; l l (ppnil lDegrce) (l 2-[ l .l .2.2-tctrachloro- 20 HI (2) lllt) i ethylsulfcnylmercapto)- fi-hydroxy pyrimidine hydrochloride 2-( l.Z.2.2-tetrachloroltlfl 2t] (1] 40 ethylsulfenylmcrcapto 4methyl pyrimidine N-methyl-N[4.6- 10 (l 91) 100 (ill (I) llh] A dimethylpyrimido-Z- sulfenyllmercapto) formamidc 2-(trich|oromcthyl 30 50 5t) sulfenylmercapto)4 methyl pyrimidine t l l Percent control refers to the eggs. In clfecl. the percent treated insects that failed to perpetuate themseltcs.

When used as an insecticide the compounds may be applied in either liquid or solid formulations to the insects. their environment or hosts susceptible to insect attack. For example. they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxic amount of one or more of the compounds and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as clay. talc. sawdust and the like may be used in such for mulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. in addition these formulations may contain other compatihle pesticides. fillers. stabilizers. attractants and the like.

The concentration of the active ingredient to be used with inert carriers. either solid or liquid carriers. will be dependent upon many factors. such as the particular compound which is used. the carrier in or upon which it is incorporated. the method and conditions of application. the insect species to be controlled. etc, the proper consideration of these factors being within the skill of those versed in the art. in general. the toxic ingredients of this invention will be effective in concentrations from about 0.000] percent by weight to as high as 50 percent by weight or higher. Economically. of course. it is desirable to use lower concentrations of this active ingredient. Thus. it is usually desirable to use less than 20 percent by weight of the active ingredient in a particular composition.

The terms *insecticide" and insect" as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus. the term insect perccntagc of treated insects that failed to reach adulthood for any reason.

is used not only to include small invertebrate animals belonging to the class lnsecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs. such as spiders. mites. ticks. centipedes. worms and the like.

As will be evident to those skilled in the art. various modifications on this invention can be made or followed. in the light of the foregoing disclosure and discussion. without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

I. A method for controlling fungi which comprises applying to said fungi or its habitat a fungicidally effective amount of the compound of the formula plus Ihose that failed to lay eggs. plus those that layed sterile wherein R is hydrogen. R and R are individually hydrogen. hydroxy or alkyl of l to 4 carbon atoms. and R is wherein R is hydrogen or alkyl of l to 4 carbon atoms and R is hydrogen. alkyl of l to 4 carbon atoms. alkenyl of 2 to 4 carbon atoms or phenyl substituted with t) to 2 halogen atoms of atomic number 9 to 35. and n is U or I.

2. The method of claim I wherein R is alkyl of l to 4 carbon atoms and R is hydrogen or alkyl of l to 4 carbon atoms.

3. The method of claim 2 wherein R is hydrogen or methyl. R is hydrogen. hydroxy or alkyl of l to 3 carbon atoms. R is ethyl and R is hydrogen.

4. The method of claim 2 wherein R is hydrogen and n is U.

5. The method of claim 4 wherein the compound is N-ethyl-N(4.6-dimethylpyrimido-2-sulfenylmercapto)formamide.

6. A fungicidal composition comprising a fungicidally effective amount of the compound of claim 1 and a biologically inert carrier.

7. The fungicidal composition of claim 6 wherein R is alkyl of l to 4 carbon atoms and R is hydrogen or alkyl of l to 4 carbon atoms.

8. The fungicidal composition of claim 7 wherein R is hydrogen or methyl. R is hydrogen. hydroxy or alkyl of l to 3 carbon atoms. R is ethyl and R is hydrogen.

9. The fungicidal composition of claim 7 wherein R is hydrogen and n is 0.

[0. The fungicidal composition of claim 9 wherein the compound is N-ethyl-Nt4,6-dimethylpyrimido-2- sulfenylmercapto)formamide. 

1. A METHOD FOR CONTROLLING FUNGI WHICH COMPRISES APPLYING TO SAID FUNGI OR ITS HABITAT A FUNGICIDALLY EFFECTIVE AMOUNT OF THE COMPOUND OF THE FORMULA
 2. The method of claim 1 wherein R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or alkyl of 1 to 4 carbon atoms.
 3. The method of claim 2 wherein R is hydrogen or methyl, R2 is hydrogen, hydroxy or alkyl of 1 to 3 carbon atoms, R4 is ethyl and R5 is hydrogen.
 4. The method of claim 2 wherein R5 is hydrogen and n is
 0. 5. The method of claim 4 wherein the compound is N-ethyl-N-(4,6-dimethylpyrimido-2-sulfenylmercapto)formamide.
 6. A fungicidal composition comprising a fungicidally effective amount of the compound of claim 1 and a biologically inert carrier.
 7. The fungicidal composition of claim 6 wherein R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or alkyl of 1 to 4 carbon atoms.
 8. The fungicidal composition of claim 7 wherein R is hydrogen or methyl, R2 is hydrogen, hydroxy or alkyl of 1 to 3 carbon atoms, R4 is ethyl and R5 is hydrogen.
 9. The fungicidal composition of claim 7 wherein R5 is hydrogen and n is
 0. 10. The fungicidal composition of claim 9 wherein the compound is N-ethyl-N-(4,6-dimethylpyrimido-2-sulfenylmercapto)formamide. 